The present invention relates to additives for preparing a straight-chain acrylonitrile dimer from acrylonitrile and to a process for preparing straight-chain acrylonitrile dimer from acrylonitrile in the presence of the additives according to the invention.
Straight-chain acrylonitrile dimers are important intermediates for preparing rust inhibitors, vulcanization processes and rubber materials. A further important area of use for straight-chain acrylonitrile dimers is the preparation of hexamethylene-diamine, which is very important for the manufacture of nylon 66.
The dimerization of acrylonitrile in the presence of ruthenium catalysts and hydrogen is described in D. T. Tsou et al., J. Mol. Catal. 22(1), 1983, 29-45. However, the presence of hydrogen gives rise to a secondary reaction in which acrylonitrile is hydrogenated to propionitrile, which is formed in major amounts (33 to 45% yield).
The dimerization of acrylonitrile in the presence of ruthenium catalysts without hydrogen atmosphere is described in DE-A-44 31 307. The dimerization is carried out using carboxylic acids as additives to suppress propionitrile formation. However, carboxylic acids have the disadvantage that they react with acrylonitrile to form xcex2-cyanoesters. This reduces the theoretically attainable yield of acrylonitrile dimer. In addition, the removal of xcex2-cyanoesters from the product mixture is only possible in time-consuming procedures. First, the xcex2-cyanoesters have to be thermally cleaved back to the starting components before these can then be removed from the products by distillation.
It is an object of the present invention to provide additives for the dimerization of acrylonitrile which suppress xcex2-cyanoesters formation and enable straight-chain acrylonitrile dimer to be formed with high selectivity. These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
It has now been found that the above-named object is achieved with additives for preparing straight-chain acrylonitrile dimer from acrylonitrile in the presence of a ruthenium catalyst, in which these additives are
(a) aromatic hydroxy compounds bearing at least one alkyloxycarbonyl substituent and at least one further substituent R on the basic aromatic structure or
(b) hetaromatic hydroxy compounds bearing at least one alkyloxycarbonyl substituent and at least one further substituent R on the basic hetaromatic structure;
in which each R is a member selected from the group consisting of halogens, cyano groups, amino groups, amido groups, urethane groups, sulphonyl groups, phosphonyl groups, formyl groups, straight-chain or branched C1-C10-alkyl groups, C1-C10-alkoxy groups, C1-C10-alkyloxo groups, C1-C10-alkylsulphinyl groups, C1-C10-alkylamino groups, C1-C10-haloalkyl groups or C1-C10-alkyloxycarbonyl groups;
and the hetaromatic hydroxy compound contains a heteroatom that is selected from nitrogen, sulphur and/or oxygen atoms.
The invention provides important benefits. Additives according to the invention, for instance, first improve straight-chain acrylonitrile dimer selectivity and secondly inhibit xcex2-cyanoesters formation completely.
The aromatic hydroxy compounds used are preferably phenol derivatives, hydroxy-naphthalene derivatives or hydroxyanthracene derivatives, particularly preferably phenol derivatives. If phenol derivatives are used as additives according to the invention, the alkoxycarbonyl substituent and/or the substituent R are disposed ortho and/or para relative to the phenolic group.
The hetaromatic hydroxy compounds used are preferably hydroxythiophene derivatives, hydroxyfuran derivatives, hydroxypyrrole derivatives, hydroxypyridine derivatives or hydroxyimidazole derivatives.
In a preferred embodiment of additives according to the invention, the alkyloxy-carbonyl substituent is straight-chain or branched C1-C10-alkyloxycarbonyl, particularly preferably methyloxycarbonyl.
R is preferably formyl, straight-chain or branched C1-C10-alkyloxo, straight-chain or branched C1-C10-alkyloxycarbonyl or straight-chain or branched C1-C10-alkyl, and the most preferred substituents R are methyloxycarbonyl, methyl, acetyl and hydroxyl.
The most preferred additives are methyl 2-hydroxybenzoate, methyl 4-hydroxy-benzoate, trimethyl 2-hydroxy-1,3,5-benzenetricarboxylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, methyl 5-acetyl-2-hydroxybenzoate or dimethyl 2-hydroxy-1,5-benzenedicarboxylate.
The invention further provides a process for preparing a straight-chain acrylonitrile dimer, which is characterized in that the acrylonitrile is dimerized in the presence of a ruthenium catalyst and in the additional presence of an additive, in which the additive includes
(a) aromatic hydroxy compounds bearing at least one alkyloxycarbonyl substituent and at least one further substituent R on the basic aromatic structure; or
(b) hetaromatic hydroxy compounds bearing at least one alkyloxycarbonyl substituent and at least one further substituent R on the basic hetaromatic structure in which each R is selected from the following: halogens, cyano groups, amino groups, amido groups, urethane groups, sulphonyl groups, phosphonyl groups, formyl groups, straight-chain or branched C1-C10-alkyl groups, C1-C10-alkoxy groups, C1-C10-alkyloxo groups, C1-C10-alkylsulphinyl groups, C1-C10-alkylamino groups, C1-C10-haloalkyl groups or C1-C10-alkyloxycarbonyl groups;
and the hetaromatic hydroxy compound contains a heteroatom that is selected from nitrogen, sulphur and/or oxygen.
In a preferred embodiment of the process of the invention, the additive and the acrylonitrile are used in a molar ratio that ranges from about 0.001:1 to about 5:1, particularly preferably from about 0.005:1 to about 2:1, most preferably from about 0.01:1 to about 0.1:1.
In a preferred embodiment of the process of the invention, the ruthenium catalysts used are ruthenium salts of organic or inorganic acids or ruthenium complexes, particularly preferably ruthenium complexes. Preferred ruthenium salts of inorganic acids are ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate and ruthenium sulphate. Preferred ruthenium salts of organic acids are ruthenium acetate, ruthenium propionate, ruthenium butanoate, ruthenium pentanoate, ruthenium hexanoate, ruthenium stearate, ruthenium naphthenate, ruthenium oxalate and ruthenium succinate. Preferred ruthenium complexes are dichloro-tetraacrylonitrile-ruthenium, dichloro-tris-(triphenylphosphine)-ruthenium, dichloro-tetrakis-(triphenylphos-phine)-ruthenium, tris-(dimethyl sulphoxide)-ruthenium, dichloro-tetrakis-(dimethyl sulphoxide)-ruthenium, dichloro-tetrakis(diphenyl sulphoxide)-ruthenium, dichloro-tetrakis-(diphenyl sulphide)-ruthenium, dibromo-dichloro-tetrakis-(dimethyl sulphoxide)-ruthenium, dichloro-tetrakis(diphenyl sulphoxide)-ruthenium, dichloro-tetrakis-(diphenyl sulphide)-ruthenium, dibromo-tetrakis-(dimethyl sulphoxide)-ruthenium, dichloro-cyclooctadiene-ruthenium, dichloro-1,4-dicyanobutadiene-ruthenium, dichloro-bis-(methyl acetylenedicarboxy-late)-ruthenium, ruthenium bis-acetylacetonate, dichloro-tris(triphenoxyphos-phine)-ruthenium and dichloro-tetrakis-(dipropyl sulphoxide)-ruthenium. The ruthenium catalyst used is most preferably dichloro-tetrakis-(diphenyl sulphoxide)-ruthenium, which is obtainable by reacting dichloro-cyclooctadiene-ruthenium with diphenyl sulphoxide in toluene.
The ruthenium catalyst used for the process of the invention is used in an amount that ranges from about 0.0001 to about 5 mol %, based on the amount of acrylonitrile used. The catalyst is preferably used in an amount that ranges from about 0.001 to about 2.5 mol %, particularly preferably from about 0.05 to about 0.1 mol %.
The linear acrylonitrile dimers preferably obtained through the process of the invention are 1,4-dicyanobutene, 1,4-dicyanobutadiene and adiponitrile.
The process of the invention makes it possible to dimerize acrylonitrile with or without a reaction medium. Preferably, the dimerization is carried out in a reaction medium. The reaction medium for the process of the invention may include nitriles, sulphoxides, ethers, hydrocarbons, halogenated hydrocarbons, amides, esters, ionic liquids or water, or mixtures thereof. The dimerization is preferably carried out in acetonitrile as reaction medium.
The process of the invention can be carried out within a temperature that ranges from about 70xc2x0 C. to about 220xc2x0 C. It is preferably carried out within the temperature ranging from about 100xc2x0 C. to about 200xc2x0 C., most preferably within the temperature range from about 110xc2x0 C. to about 180xc2x0 C.
The reaction pressure for the process of the invention is customarily within the range from about 0.1 bar to about 50 bar. It is preferably carried out within the range from about 1 bar to about 30 bar, particularly preferably from about 5 bar to about 25 bar.
In a preferred embodiment of the process of the invention, acrylonitrile is dimerized in the presence of dichloro-tetrakis-(diphenyl sulphoxide)-ruthenium and in the presence of the additive dimethyl 2-hydroxy-1,5-benzenedicarboxylate, in acetonitrile as a reaction medium.
The invention is further described in the following illustrative examples in which all parts and percentages are by weight unless otherwise indicated.